Recovery of vanadim and nickel from petroleum



Sept. 4, 1945. M. c. K. JONES 2,383,972

RECOVERY OF VANADIUM AND NICKEL FROM PETROLEUM Filed June 12, 1940 $CON.DARY BUBBLE TOM/7? 7%? mm Y Zuzana rowa EVAPORA TOR 7 P526 TORE.

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CL 7254 NT UNIT f f/EA w/vc co IL gm i ri w r j i is w r brac sa tg s a metaiu stantially coifiblgtely p11; contagmng t fich 9 .9 ils controllii to produceafi overhead distillate of the desired and point. This distillate is removed boiling range, are removed from the bottomof secondary bubble tower i2. passed through cooler i8, and withdrawn from the system by line 20.

Tar or heavy fuel oil containing the zeolite and the metallic constituents is removed from the bottom of evaporator 9 by means of line 32 and passed through temperature control unit 33. in

which it is possible to either raise or lower the temperature of the tar or heavy fuel oil fraction to the desired degree. The heavy oil fraction is withdrawn from. the temperature control unit a and passed into separator 34 which may commeans of ther characterized in that the reagent will not prise any suitable number of units of any desired design, in which the zeolite is separated from the heavy fuel oil or tar fraction. The tar or fuel oil fraction is withdrawn from the system by means of line it and handled in any manner desired. The zeolite containing the metallic constituents is withdrawn from separator 34 which may comprise a metallic screen filter by meansof line '30 and handled to remove and recover the metallic constituents from the zeolite by suitable means. This is preferably accomplished by passing the zeolite to a solvent washing unit 50 in which the tarry oil fractions are removed from the zeolite by washing with a solvent which is introduced by means of line It and withdrawn by means of line 52.. The zeolite substantially free of oily constituents is withdrawn from washing unit 50 by means of line 53 and handled in a manner to remove and recover the metallic constituents from the zeolite. This is preferably accomplished by treating the zeolite with a solvent having the ability to partially dissolve the metallic constituents from the zeolite. Solvents of this class are for example various diluted solutions of mineral acids as for example sulfuric, hydrochloric and nitric acid. The zeolite, free of recovered metallic constituents, is removed from recovery unit 31 by means of line 30, regenerated, and recycled to the system. Following the acid treatment, the reagent becomes a hydrogen 'zeolite and it is treated with a brine suchas a sodium chloride brine to regenerate the zeolite and form the sodium zeolite. Although the step of regenerating the reagent may be employed in applicant's novel process and forms a valuable adjunct thereto. it is not per se novel. The solution of recovered metallic constituents is removed from unit 31. by meansof line I! andpassed to solvent recovery unit I! in which the solutions are handled in a manner to recover the metallic constituents. The solvent, as desired, may be recycled to the recovery unit by means of line Iii, while the recovered metallic constituents may be withdrawn from the system by means of line H.

The process of the invention may be widely varied. In general the invention is concerned with a process adapted to the recovery of metallic constituents of the class consisting of molybdenum, vanadium, nickel and zinc from mineral oils, particularly from petroleum oils containing affect the normal refining operation. Suitable solid reagents are for example (1) mixtures of sodiumcarbonate and various clays such as kaolin, (2) zirconium oxide, (3) kaolin alumina mixtures, (4) diatomaceous earths, (5) alkali metal salts such as sodium carbonate and potassium carbonate, and (6) the salts of iron and lead which form lead vanadates and ferric vanadates and the like. A particularly desirable material comprises molten sulfur which precipitates out of the tar along with the vanadium upon cooling. However, in general thepreferred solid reagents are selectedfrom the class of alkali metal aluminum silicates of the zeolite type, especially the naturally occurring hydrated alkali metal aluminum silicates, as for example a naturally occurring hydrated sodium aluminum silicate having the formula Nfl-HsAlSlOr.

The temperatures and pressures will be a function of the characteristics of the particular; feed oil, and will also depend upon the concentration of themetallic compounds present as well as upon the type of reagent employed. Whenutilizing a zeolite, the temperature and pressure conditions are generally in the range at which substantially no decomposition of the oil occurs due to the efiect of the zeolite. In general the temperatures are in the range from about 250 to 800 ll, but higher temperatures in the range above about 1000 F., are preferred and the pressures vary from atmospheric to oil cracking pressures. It is preferred that the pressures be in the range from about to 1000 lbs/sq. in.

, The metallic constituent may be recovered from the product resulting from the reaction with the reagent by processes essentially involved in solvent treatment or roasting. For example, if

sulfur be used as the reagent, the vanadium may be recovered from the sulfide by roasting to produce the vanadium oxide and then reduced to substantially pure vanadium by a selective furnace roasting'reaction. Ii zeolite be employed, the vanadium is extracted by solvent treating the zeolite wltha strong mineral acid as for example a strong solution of hydrochloric or sulfuric acid. The vanadium is precipitated from the acid solution preferably as ammonium vanadate by evaporating the acid solution with an excess of ammonium chloride. 7 The ammonium vanedate is then'roasted to produce the oxide which may be reduced by means of an electric furnace.

The solid absorbent containing the recovered the vanadium present. Upon withdrawal of the tar, the reagent is allowed to settle while the tar is still hot and limpi The reagent is removed and again employed for the recovery of vanadium inthe manner described, The solvent employed for removing the occluded tarry oil fractions from the solid absorbent containing the vanadi um after separation from the tarry fraction is preferably a relatively low boiling petroleum oil fraction. A particularly desirable solvent comprises a petroleum oil fraction boiling in the range from about 300 F. to 450 F. Under certain operations it may be desirable to remove the tarry fractions from the absorbent by burning.

In order to more fully illustrate the invention, the following examples are given which should not be construed to restrict the same in any manner whatsoever.

Example 1 A feed oil representing the highest 8% boiling fraction of a Lake Venezuela, crude oil was passed over pumice at a temperature of about 900 F., at a velocity of about 23 feet per second. Analysis of the treated oil after 4800 units were treated indicated that substantially complete removal of the vanadium from the oil wassecured and that the vanadium content of the pumice was about 0.24%.

Example 2 A reduced Venezuela Lagunillas crude was passed over a mixture comprising 50% sodium carbonate and 50% kaolin at a temperature of about 780 F. to 820 F. and at atmospheric pres- Sure. The feed rate employed was 1.2 volumes of oil per volume of. catalyst per hour. At thetallic constituents of the class consisting of molybdenum, vanadium, nickel and zinc from petroleum oils containing the same, and for the production of relatively higher and relatively lower boiling petroleum oil constituents by cracking, which comprises mixing the said petroleum oil with a solid reagent selected from the class of naturally occurring hydrated alkali metal aluminum silicates of the zeolite type, passing the feed oil through heating means adapted to raise the oil to the desired cracking temperature and pressure level, maintaining the feed oil under the desired conditions for the optimum time period, then passing the same through a pressure release valve into an evaporator adapted to concentrate a relatively small quantity of the relatively higher boiling constituents, removing the relatively higher boiling constituents along with the solid reagent containing the desired metallic constituents from the bottom of said evaporator, physically separating the relatively higher boiling constituents from the solid reagent containing the metallic constituents, and recovering the metallic constituents therefrom.

2. Process for the separation and recovery of vanadium from petroleum oils containing the same and for the production of relatively higher and relatively lower boiling petroleum oil constituents which comprises mixing the feed petroleum oil with a solid reagent selected from the class of alkali metal aluminum silicates of the zeolite type, which will react with the vanadium and which will not substantially afiect the refining operation, passing the feed oil through heating means adapted to raise the oil to the desired cracking temperature and pressure level, maintaining the feed oil under the desired conditions for the optimum time period, then passing the oil through a. pressure release valve into an evaporator adapted to concentrate a relatively small quantity of the relatively higher boiling constituents, removing the relatively higher boiling constituents along with the zeolite containing the vanadium, and recovering the vanadium therefrom.

3. Process for the separation and recovery of vanadium from mineral oils containing the same which comprises contactingthe feed mineral oil with an alkali metal aluminum silicate of the zeolite type at an elevated temperature and pressure, which deposits a coating of relatively high boiling mineral oil constituents upon the zeolite, separating the zeolite from the mineral oil, treating the zeolite with a relatively low boiling petroleum oi1 solvent to remove relatively high boiling mineral oil constituents therefrom, separating the zeolite containing the vanadium and recovering the vanadium therefrom.

4. A process according to claim 3 wherein the separated zeolite type reagent is regenerated and recycled to the oil treating step for removal of additional amounts of vanadium from fresh mineral oils.

MINOR C. K. JONES. 

